The microstructures and their thermal behaviors of quenched Al94V4Fe2, Al90V8Fe2, Al86V8Fe6, and Al85V9Fe2Ni4 alloys were investigated by x-ray diffraction, transmission electron microscopy, and differential scanning calorimetry. The as-quenched microstructures of the four alloys consist of quasicrystal particles and a fcc-α–Al matrix. The as-quenched Al86V8Fe6 and Al85V9Fe2Ni4 alloys also contain a small volume fraction of amorphous phase. All phases observed have fine morphologies with grain sizes of less than 100 nm. With the increase in V from 4 to 8 at.% at 2 at.% Fe, the average grain size decreases from 100 to 70 nm and the melting temperature of α–Al solid solution increases from 640 to 653 °C. The alloy with 8 at.% V has a finer and more stable microstructure than that of the alloy with 4 at.% V. The Fe addition has minor effect on grain size but improves the glass-forming ability. The Ni addition significantly improves the glass-forming ability and refines the microstructure. The metastable amorphous and quasicrystalline phases transform into a stable crystalline phase during continuous heating and cooling. The stable phases in these Al–V–Fe alloys include α–Al(V, Fe), Al10V, and Al80V12.5Fe7.5.